CN102403069B - A kind of preparation method of titanium dioxide/titanium wire composite electrode - Google Patents

A kind of preparation method of titanium dioxide/titanium wire composite electrode Download PDF

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CN102403069B
CN102403069B CN201110338368.5A CN201110338368A CN102403069B CN 102403069 B CN102403069 B CN 102403069B CN 201110338368 A CN201110338368 A CN 201110338368A CN 102403069 B CN102403069 B CN 102403069B
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titanium
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tio
combination electrode
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董祥
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Kunming University of Science and Technology
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Abstract

The invention provides a kind of preparation method of titanium dioxide/titanium wire composite electrode, by the process of titanium base material, the preparation of titanium silk surface nano-titanium dioxide combination electrode, the heat treatment of combination electrode, namely obtain nano titanium oxide/titanium silk combination electrode.The present invention can realize being attached to the nano-TiO of different conductive filament, the crystalline one-dimension oriented growth of line suprabasil titanium film in-situ preparation or non-oriented growth 2as long as this substrate/titanium film/nano-TiO just can be obtained by one step hydro thermal method 2or Titanium base/nano-TiO 2structure, wherein titanium film as excellent conductive layer, can expand its range of application greatly.

Description

A kind of preparation method of titanium dioxide/titanium wire composite electrode
Technical field
The present invention relates to a kind of hydrothermal reaction at low temperature and prepare one dimension in order or the method for the nano titanium oxide/titanium silk combination electrode of random growth, belong to semiconductor functional electrode technology field.
Background technology
Nano-TiO 2it is a kind of important inorganic functional material, because having the advantages such as the photocatalysis performance of photoelectric conversion, air-sensitive, dielectric effect and excellence, make it have important application prospect in fields such as solar cell, transducer, dielectric material, self-cleaning material and photocatalysis to degrade organic matter, and improve and reinforced nano TiO 2these proper properties just become domestic and international scientific research personnel pursue target.Usual reinforced nano TiO 2the method of performance has: doping, compound, sensitization, structure regulating etc., wherein structure regulating does not change nano-TiO because of it 2inherent characteristic, and performance enhancing effects is remarkable etc., and feature becomes the focus studied in recent years.Many researchers is all devoted to the TiO preparing different-shape and structure 2nanometer, micron thing, such as nanotube, nanometer rods, nano wire, multilevel hierarchy nanometer thing etc. (ZhangQF, CaoGZ.NanoToday, 2011,6:91-109.).The nano-TiO of these special constructions 2have large specific area, excellent optical property, and good electronic conduction ability, thus more reactivity point is provided, improve the utilance of incident light, and reduce the recombination rate of light induced electron, therefore can significantly improve nano-TiO 2correlated performance.
Generally speaking, the alkoxide of titanium or the halide of titanium etc. are used as preparation TiO 2the predecessor of nanometer thing, but often cost is higher for this kind of material, and easily pollution is produced to environment.The process of predecessor simultaneously needs multiple step, wastes time and energy.Therefore, pure titanium is selected as predecessor to prepare nano-TiO 2a kind of method of simple possible is not only by combination electrode, and grows the nano-TiO of ad hoc structure in titanium surface hydro-thermal 2directly can be prepared into electrode to use, overcome nano-TiO 2second electrode procedure of processing in application, also solves nano-TiO simultaneously 2be difficult to the problem recycled.But the kind of hydrothermal solution and concentration prepare ad hoc structure nano-TiO 2key factor.
At present, nano-TiO is prepared using pure titanium as titanium source 2mostly adopt hydro thermal method or solvent-thermal method preparation.Calendar year 2001, American scientist Varghese utilized the method for electrochemical oxidation, had prepared TiO first in titanium sheet 2nano-tube array (DaweiG, et.al, J.Mater.Res., 2001,16:3331), carries out the nano-tube array that high-temperature heat treatment obtains crystallization subsequently, and shows excellent air-sensitive, photocatalysis performance.Within 2005, PENGX. utilizes the method for thermal oxidation high-temperature oxydation in titanium substrate to prepare TiO 2nanometer stick array (PENGX., Appl.Phys.A, 2005,80:473), the method needs two step heated oxides, and needs under inert atmosphere protection, to carry out high-temperature oxydation, therefore complex procedures, high to equipment requirement.At 2005,2006, the Wu Jinming of Zhejiang University has applied for that, about pickling metal titanium plate, in hydrogen peroxide solution, hot water prepares TiO 2the patent (Wu Jinming, CN200510060751, CN200610052743.9) of nanometer stick array, the hydrothermal solution used in these two patents is all the hydrogen peroxide solution of one-component.The research group of GuoY.P and KimS.J in 2008 adopts the method for hydro-thermal to prepare the TiO of oriented growth in titanium sheet substrate 2nano-tube film layer (GuoY.P., et.al., ThinSolidFilm, 2008,516:8363), and the work electrode of lithium ion battery just can be used as through simple process, enhance capacity and the speed of discharge and recharge, prepare the nano-TiO of special construction as can be seen here using pure titanium as predecessor on its surface 2thin layer, by the structure improving performance of thin layer, can not only can also utilize titanium substrate to be prepared into electrode, avoid nano-TiO 2electrode secondary processing process in application.2009, the research group of NovakS. grown the TiO of one deck Detitanium-ore-type in titanium alloy (Ti6A4V) surperficial hydro-thermal 2nanometer layer is as the functional coating (DrnovsekN., Surface & CoatingTechnology, 2009,203:1462) of titanium alloy artificial skelecton, and result shows nano-TiO 2layer and titanium alloy combine tight, effectively can reduce the cytotoxicity that Ti and titanium alloy cause in human body.This shows that be not only can hydrothermal growth nano-TiO in pure titanium substrate 2, the alloy of titanium can grow equally fine and close, the nano-TiO of mechanical performance excellence 2layer.
As can be seen here, TiO is prepared using pure titanium, titanium alloy as titanium source hydro thermal method 2nanometer thing has simply, the feature of low cost, a step can just prepare crystalline nano-TiO 2, nano-TiO simultaneously 2structure and pattern also there is controllability.In addition, nano-TiO 2original position forms in pure titanium superficial growth, and pure titanium layer is as nano-TiO 2the contact layer of film, then can ensure nano-TiO 2thin layer has good mechanical performance.Other materials are selected often to cause nano-TiO as substrate 2between film and substrate in conjunction with bad, thus affect its application performance.
Can find out from above summary adopts hydro thermal method to prepare the nano-TiO of oriented growth or non-oriented growth on the pure titanium surface of two dimensional surface 2existing relevant research, but at the nano-TiO that the cylindrical pure titaniums of one dimension such as titanium silk, line, rod, titanium alloy surface preparation orientation or non-directional grow 2film have not been reported.At titanium silk surface hydrothermal growth special construction nano-TiO 2thin layer, can be prepared into the work electrode of wire, and this electrode structure can be divided into two levels, and the first level is the nano-TiO on titanium silk surface 2thing, such as: perpendicular to the epontic 1-dimention nano TiO of titanium silk 2array, the 1-dimention nano TiO being attached to titanium silk surface that the second level is made up of nanometer thing 2film, does not consider titanium silk carrier, and this film is a kind of tubular film.This thread combination electrode can further expand nano-TiO 2range of application, be prepared into the work electrode being applicable to particular device, such as: the solar cell of concentric shafts, high-sensitive gas sensor etc., and the combination electrode that can be prepared into ad hoc structure in advance after bent rich titanium silk.On the other hand, at titanium silk surface hydro-thermal growing nano TiO 2its technological difficulties are: (1) is difficult to be controlled at the orientation of curved surface growth nano titania thing, must grow, but this method is loaded down with trivial details, and requires higher to instrument and equipment by means of template or orientated deposition; (2) although hydro thermal method is simple and practical, the kind of hydrothermal solution and concentration prepare single-orientated TiO 2two large key factors of nanometer stick array.Generally speaking, hydro-thermal reaction does not have directed dimension growth characteristics, and simultaneously product grows in three dimensions, and product is particle often.Be prepared in the product of specific dimension growth, the growth of special solution ability restrictive substance on other dimension directions of apparatus oriented attachment must be made, ensure the growth of material on specific dimension direction.In addition, the concentration of solution can affect the direction that reaction rate and reaction are carried out.First be that material is dissolved by hydrothermal solution in hydro-thermal reaction, then forming core growth under high-temperature and high-pressure conditions, solubilizing reaction is for crystalline growth provides crystal growth raw material, and crystalline growth is then consume raw material.Therefore, under suitable solution concentration, " output " and " consumption " of raw material these two process balances only just can be made to carry out, thus ensure that product has unified orientation, otherwise the structure of uncontrollable product and orientation.
Summary of the invention
For overcoming the problems such as method in prior art is loaded down with trivial details, equipment requirement is high, energy consumption is large, the invention provides a kind of preparation method of titanium dioxide/titanium wire composite electrode, with hydrothermal reaction at low temperature preparation, there is the nano titanium oxide/titanium silk combination electrode of special construction and pattern on titanium silk surface, the method can prepare unified orientation, non-oriented with substrate, there is the nano titanium oxide/titanium silk combination electrode of good combination power.
The present invention is realized by following technical proposal: a kind of preparation method of titanium dioxide/titanium wire composite electrode, through following each step:
A. the process of titanium base material: first titanium silk is rinsed successively in acetone, absolute ethyl alcohol, water, then titanium silk is soaked 1 ~ 60min in mixed solution, then rinse post-drying with water;
B. the preparation of titanium silk surface nano-titanium dioxide combination electrode: alkaline solution put into by the titanium silk after being dried by steps A gained, and be 1 ~ 20 DEG C/min with the rate of heat addition, after being heated to 60 ~ 280 DEG C, be incubated 1 ~ 120h again, then be cooled to room temperature, take out from alkaline solution and obtain combination electrode;
C. the heat treatment of combination electrode: rinsed by the combination electrode use water of step B gained, then soaks 2 ~ 72h in the acid solution of 0.01 ~ 5mol/L; Take out use water again to rinse, and be warming up to 300 ~ 700 DEG C with 1 ~ 20 DEG C/min speed in air atmosphere, then be incubated 0.5 ~ 4h, then cool to room temperature, after taking-up, namely obtain nano titanium oxide/titanium silk combination electrode.
The titanium silk of described steps A is titanium or the titanium alloy wire of Ti content more than 50% of TA, TB, TC series, or be covered with pure titanium layer by surface prepared by magnetron sputtering, evaporation, atom sediment, inner core is the clad metal wire of other good conductors of electricity.
The hydrofluoric acid Rong Ye ︰ concentration of the mixed solution of described steps A to be concentration be 1 ~ 38.2wt% is the volume ratio of the Xiao Suan Rong Ye ︰ water of 1 ~ 65wt% is 1 ︰ 1 ~ 10 ︰ 5 ~ 100.
Alkaline solution in described step B is that one or more in organic alkali solution or inorganic alkali solution mix arbitrarily, as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, ammoniacal liquor, NaOH, potassium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, alkaline solution concentration is 0.001 ~ 10mol/L.
Acid solution in described step C is sulfuric acid, hydrochloric acid or aqueous solution of nitric acid.
Described water is distilled water and deionized water.
The beneficial effect that the present invention possesses and advantage:
1, the present invention can realize being attached to the crystalline nano-TiO with orientation or non-oriented growth of titanium film in-situ preparation of (as aluminium wire, stainless steel wire, silicon silk) in one dimension wire different base 2film, as long as just can obtain this substrate/titanium film/nano-TiO by one step hydro thermal method 2or Titanium base/nano-TiO 2structure, wherein titanium film as excellent conductive layer, can expand its range of application greatly;
2, the alkaline solution of one-component and various ingredients can realize TiO 2the morphology controllable of nanometer rods.Nano-TiO 2pattern, structure and size change can bring the change of performance, particularly can by regulation and control TiO 2the ratio of particular crystal plane in whole crystal, thus realize the controllability of its performance, to meet the application requirement of multiple one dimension wire electrode;
3, the present invention has that cost is low, simple to operate, processing step is few, the advantage of titanium dioxide product perfect crystalline.Every reaction solution can infiltrate the pure titanium region arrived, and just can generate active nano titanic oxide thin layer, makes complex-shaped flexible electrode of can bently having mercy on, overcomes the drawback that the conventional physical methods such as magnetron sputtering cannot realize processing wire electrode 360o simultaneously.
Accompanying drawing explanation
Fig. 1 is the one dimension TiO of the radially oriented growth of the nano titanium oxide/titanium silk combination electrode of embodiment 1 gained 2nano-wire array scanning electron microscope (SEM) photograph;
Fig. 2 is the one dimension TiO of the nano titanium oxide/titanium silk combination electrode of embodiment 2 gained 2the membrane scanning electron microscope (SEM) photograph of nanometer;
Fig. 3 is the one dimension TiO of the oriented growth of the nano titanium oxide/titanium silk combination electrode of embodiment 1 gained 2nano-wire array X-ray diffractogram;
Fig. 4 is the one dimension TiO of the nano titanium oxide/titanium silk combination electrode of embodiment 2 gained 2the membrane X-ray diffractogram of nanometer;
Fig. 5 is the scanning electron microscope (SEM) photograph of the nano titanium oxide/titanium silk combination electrode of embodiment 3 gained.
Embodiment
Illustrate content of the present invention further below in conjunction with embodiment, but these examples do not limit the scope of the invention.
Embodiment 1
A. first the titanium silk of TA series is rinsed successively in acetone, absolute ethyl alcohol, distilled water, again titanium silk is soaked 15min in mixed solution, wherein, the hydrofluoric acid Rong Ye ︰ concentration of mixed solution to be concentration be 38.2wt% is the volume ratio of the Xiao Suan Rong Ye ︰ distilled water of 65wt% is 1 ︰ 1 ︰ 5; Dry at 70 DEG C with after distilled water flushing 1min again;
B. the titanium silk after being dried by steps A gained is put into sodium hydroxide solution that concentration is 3mol/L and is 1 DEG C/min with the rate of heat addition, after being heated to 200 DEG C, then is incubated 12h, is then cooled to room temperature, takes out and obtain combination electrode from alkaline solution;
C. by the combination electrode of step B gained distilled water flushing 3 times, then at the aqueous hydrochloric acid solution of 1mol/L) in soak 24h; Take out again and use deionized water rinsing 3 times, and be warming up to 450 DEG C with 5 DEG C/min speed in air atmosphere, then be incubated 2h, then cool to room temperature, after taking-up, namely obtain nano titanium oxide/titanium silk combination electrode.
Testing result: as shown in Figure 1, titanium silk surface is by TiO 2nano wire covers, TiO 2nano wire has the unified orientation radially grown; And TiO 2the diameter of nano wire is at about 40nm, TiO 2the length of nano wire is at about 2600nm, and arrangement very well, vertical substrate grown.Shown by the result of Fig. 3, TiO 2nano wire is Detitanium-ore-type monocrystal.
Embodiment 2
A. first the titanium silk of TB series is rinsed successively in acetone, absolute ethyl alcohol, distilled water, again titanium silk is soaked 1min in mixed solution, wherein, the hydrofluoric acid Rong Ye ︰ concentration of mixed solution to be concentration be 1wt% is the volume ratio of the Xiao Suan Rong Ye ︰ distilled water of 30wt% is 1 ︰ 10 ︰ 100; Dry at 70 DEG C with after distilled water flushing 1min again;
B. the potassium hydroxide solution that concentration is 1mol/L put into by the titanium silk after being dried by steps A gained, and is 10 DEG C/min with the rate of heat addition, after being heated to 220 DEG C, then is incubated 12h, is then cooled to room temperature, takes out and obtain combination electrode from alkaline solution;
C. by the combination electrode of step B gained distilled water flushing 3 times, then in the aqueous hydrochloric acid solution of 1mol/L, 24h is soaked; Take out again and use distilled water flushing 3 times, and be warming up to 500 DEG C with 5 DEG C/min speed in air atmosphere, then be incubated 1h, then cool to room temperature, after taking-up, namely obtain nano titanium oxide/titanium silk combination electrode.
Testing result: as shown in Figure 2, titanium silk is epontic is one dimension TiO 2nanobelt, the width of band is at about 40nm, and thickness is at about 10nm; Shown by the result of Fig. 4, TiO 2nanobelt is single anatase crystal.
Embodiment 3
A. first the surface of being prepared by magnetron sputtering, evaporation, atom sediment is covered with pure titanium layer, inner core is stainless clad metal wire ultrasonic cleaning 15min in acetone, absolute ethyl alcohol, distilled water successively, again titanium silk is soaked 60min in mixed solution, wherein, the hydrofluoric acid Rong Ye ︰ concentration of mixed solution to be concentration be 20wt% is the volume ratio of the Xiao Suan Rong Ye ︰ distilled water of 1wt% is 1 ︰ 5 ︰ 50; Use distilled water flushing post-drying again;
B. the alkaline solution that concentration is 10mol/L put into by the titanium silk after being dried by steps A gained, wherein, alkaline solution is the mixed solution of Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, and be 20 DEG C/min with the rate of heat addition, after being heated to 180 DEG C, be incubated 24h again, be then cooled to room temperature, take out from alkaline solution and obtain combination electrode;
C. by the combination electrode distilled water flushing of step B gained, then in the aqueous solution of nitric acid of 0.01 ~ 5mol/L, 24h is soaked; Taking-up deionized water rinsing again, and 450 DEG C are warming up to 5 DEG C/min speed in air atmosphere, then be incubated 1h, then cool to room temperature, namely obtain nano titanium oxide/titanium silk combination electrode after taking-up.
Testing result: as shown in Figure 5, the nano wire film of the No yield point growth that titanium silk surface coverage is a large amount of.The diameter of line is at about 30nm.
Embodiment 4
A. first the titanium alloy wire of Ti content more than 50% is rinsed successively in acetone, absolute ethyl alcohol, deionized water, again titanium silk is soaked 60min in mixed solution, wherein, the hydrofluoric acid Rong Ye ︰ concentration of mixed solution to be concentration be 30wt% is the volume ratio of the Xiao Suan Rong Ye ︰ deionized water of 60wt% is 1 ︰ 10 ︰ 90; Use deionized water rinsing post-drying again;
B. the alkaline solution that concentration is 0.001mol/L put into by the titanium silk after being dried by steps A gained, wherein, alkaline solution is the mixed solution of calcium hydroxide, barium hydroxide, magnesium hydroxide, and be 15 DEG C/min with the rate of heat addition, after being heated to 60 DEG C, be incubated 120h again, be then cooled to room temperature, take out from alkaline solution and obtain combination electrode;
C. by the combination electrode deionized water rinsing of step B gained, then at the sulfuric acid solution of 0.01mol/L) middle immersion 72h; Taking-up deionized water rinsing again, and 300 DEG C are warming up to 1 DEG C/min speed in air atmosphere, then be incubated 4h, then cool to room temperature, namely obtain nano titanium oxide/titanium silk combination electrode after taking-up.
Embodiment 5
A. first the titanium silk of TC series is rinsed successively in acetone, absolute ethyl alcohol, deionized water, again titanium silk is soaked 40min in mixed solution, wherein, the hydrofluoric acid Rong Ye ︰ concentration of mixed solution to be concentration be 38.2wt% is the volume ratio of the Xiao Suan Rong Ye ︰ deionized water of 55wt% is 1 ︰ 8 ︰ 20; Use deionized water rinsing post-drying again;
B. the alkaline solution that concentration is 10mol/L put into by the titanium silk after being dried by steps A gained, wherein, alkaline solution is the mixed solution of TBAH, ammoniacal liquor, and be 15 DEG C/min with the rate of heat addition, after being heated to 280 DEG C, be incubated 1h again, be then cooled to room temperature, take out from alkaline solution and obtain combination electrode;
C. by the combination electrode distilled water flushing of step B gained, then in the aqueous solution of nitric acid of 5mol/L, 2h is soaked; Taking-up distilled water flushing again, and 700 DEG C are warming up to 20 DEG C/min speed in air atmosphere, then be incubated 0.5h, then cool to room temperature, namely obtain nano titanium oxide/titanium silk combination electrode after taking-up.

Claims (4)

1. a preparation method for titanium dioxide/titanium wire composite electrode, is characterized in that through following each step:
A. the process of titanium base material: first titanium silk is rinsed successively in acetone, absolute ethyl alcohol, water, again titanium silk is soaked 1 ~ 60min in mixed solution, rinse post-drying with water again, wherein the hydrofluoric acid Rong Ye ︰ concentration of mixed solution to be concentration be 1 ~ 38.2wt% is the volume ratio of the Xiao Suan Rong Ye ︰ water of 1 ~ 65wt% is 1 ︰ 1 ~ 10 ︰ 5 ~ 100;
B. the preparation of titanium silk surface nano-titanium dioxide combination electrode: alkaline solution put into by the titanium silk after being dried by steps A gained, and be 1 ~ 20 DEG C/min with the rate of heat addition, after being heated to 60 ~ 280 DEG C, be incubated 1 ~ 120h again, then room temperature is cooled to, take out from alkaline solution and obtain combination electrode, wherein, alkaline solution is Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, ammoniacal liquor, NaOH, potassium hydroxide, calcium hydroxide, barium hydroxide, one or more in magnesium hydroxide mix arbitrarily, alkaline solution concentration is 0.001 ~ 10mol/L,
C. the heat treatment of combination electrode: rinsed by the combination electrode use water of step B gained, then soaks 2 ~ 72h in the acid solution of 0.01 ~ 5mol/L; Take out use water again to rinse, and be warming up to 300 ~ 700 DEG C with 1 ~ 20 DEG C/min speed in air atmosphere, then be incubated 0.5 ~ 4h, then cool to room temperature, after taking-up, namely obtain nano titanium oxide/titanium silk combination electrode.
2. preparation method according to claim 1, it is characterized in that: the titanium silk of described steps A is titanium or the titanium alloy wire of Ti content more than 50% of TA, TB, TC series, or be covered with pure titanium layer by surface prepared by magnetron sputtering, evaporation, atom sediment, inner core is the clad metal wire of other good conductors of electricity.
3. preparation method according to claim 1, is characterized in that: the acid solution in described step C is sulfuric acid, hydrochloric acid or aqueous solution of nitric acid.
4. according to the preparation method in claims 1 to 3 described in any one, it is characterized in that: described water is distilled water and deionized water.
CN201110338368.5A 2011-11-01 2011-11-01 A kind of preparation method of titanium dioxide/titanium wire composite electrode Expired - Fee Related CN102403069B (en)

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CN1544684A (en) * 2003-11-24 2004-11-10 甘 宪 Process for preparing titanium dioxide film on metal Ti surface and Ti plate with titanium dioxide film coated surface prepared thereby
CN101343746A (en) * 2008-08-28 2009-01-14 上海交通大学 Titanium oxide nano wire film on metallic titanium surface and manufacture method thereof
CN101525152A (en) * 2008-12-16 2009-09-09 中国科学院电工研究所 Mumm-shaped 3D TiO nanometer material and preparation method thereof
CN101768771A (en) * 2008-12-31 2010-07-07 北京大学 Cylindrical and barrel-shaped titanium dioxide nanotube arrays and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN1544684A (en) * 2003-11-24 2004-11-10 甘 宪 Process for preparing titanium dioxide film on metal Ti surface and Ti plate with titanium dioxide film coated surface prepared thereby
CN101343746A (en) * 2008-08-28 2009-01-14 上海交通大学 Titanium oxide nano wire film on metallic titanium surface and manufacture method thereof
CN101525152A (en) * 2008-12-16 2009-09-09 中国科学院电工研究所 Mumm-shaped 3D TiO nanometer material and preparation method thereof
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